Photographic silver halide element having improved storage stability

ABSTRACT

The invention provides a multilayer silver halide color negative photographic element comprising in the same layer a cyan dye of formula (I) and a ballasted stabilizer compound of formula (II), where the respective formulas are:    &lt;IMAGE&gt;  (I)  andB-L-A-R(II)wherein: the substiuents are as defined herein the specification.

FIELD OF THE INVENTION

This invention relates to a multilayer silver halide photographicelement containing in the same layer a naphtholic cyan dye of formula(I) and a ballasted stabilizer of formula (II). Such an element exhibitsimproved storage stability.

BACKGROUND OF THE INVENTION

Modern color negative films usually contain dyes coated in one or morelayers for a variety of purposes. In addition to being utilized forspectral sensitization, dyes may be used for other purposes such asfiltering specific wavelengths of exposing light (either as intergrainabsorbers or in separate layers containing no silver halide), forantihalation and for adjusting the background density (Dmin) of colornegative films for printing purposes. Such preformed coated dyes (thatis, dyes which are present in the element prior to exposure anddevelopment) are often referred to as "dummy dyes" to distinguish themfrom dyes that are formed photographically as a result of exposure andchromogenic development.

In the development of color photographic elements, bleach solutions areused to oxidize developed silver to silver ions for subsequent removalin fix solution by formation of soluble silver complexes. The bleach andfix solutions are sometimes combined into a single "blix" solution.Bleach solutions commonly contain complexes of ferric ion, such asferric ethylenediaminetetraacetic acid (EDTA), as oxidizing agents.Prolonged use of such solutions for processing of photographic film canresult in accumulation of substantial quantities of the correspondingferrous ion complexes (such as ferrous EDTA), which can function asreducing agents. These reducing agents can cause reductive discolorationof dummy dyes (so called leuco dye formation). The formation of leucodye in such seasoned bleaches is undesirable, not only because theresulting Dmin density provided by the dummy dye will be less than theoptimum required for proper printing characteristics, but also becausevariabilities in Dmin can occur as seasoning of a bleach progresses.

Many cyan dyes that have been used in color negative films forantihalation and for Dmin adjustment have suffered from a number ofdeficiencies, including loss of color in seasoned photographic bleachsolutions or in bleaches of low oxidizing strength. Additionally, theymay also have improper hue or suffer from changes in hue and/or densityupon storage at low or high temperatures. For example, the dye ofstructure: ##STR2## has been used extensively in a number of commercialcolor negative films. The hue of this dye is suitable for Dminadjustment and for antihalation purposes. However, this dye can undergoreductive discoloration when films containing it are processed inseasoned photographic bleaches or in bleaches of weak oxidizing power.

Merkel et al., U.S. Pat. No. 5,460,930 proposes an improved naphtholicdye which exhibits less tendency to undergo leuco dye formation inseasoned bleaches or weak bleaches. However, dyes having the formula ofthe Merkel patent and dyes similar thereto exhibit an undesirablestorage instability or keeping problem. These dyes cause elevatedminimum density (Dmin), particularly when the element containing the dyeis subjected to high temperatures or long storage times.

It is a problem to be solved to provide a multilayer photographicelement containing naptholic cyan dyes of either of the types describedwhich have improved storage stability.

SUMMARY OF THE INVENTION

The invention provides a multilayer silver halide color negativephotographic element comprising in the same layer a cyan dye of formula(I) and a ballasted stabilizer compound of formula (II), where therespective formulas are: ##STR3## wherein: R1 is selected from the groupconsisting of an alkoxy group, a phenoxy group and a halogen atom;

R2 is selected from the group consisting of hydrogen, an alkyl group, aphenyl group; a halogen atom, an alkoxy carbonyl group of formula--COOR7, and a carbonamido group of formula --NR8COR7;

R3, R4, R5 and R8 are independently selected from the group consistingof hydrogen and an alkyl group;

R6 is an alkyl group; and

R7 is an alkyl group or a phenyl group;

and

    B--L--A--R                                                 (II)

wherein:

B is a ballast group;

L is a divalent linking group;

A is a group of the formula: ##STR4## wherein R' is hydrogen or an alkylor alkoxy group; and

R is hydrogen or an aliphatic or aromatic group linked directly orthrough a nitrogen or oxygen atom to A.

The invention also provides a method of forming a color negative imageon a transparent support using the element of the invention and aprocess for obtaining a positive image by using an exposed and developednegative element of the invention to optically print a positive imageonto a second color. negative element.

DETAILED DESCRIPTION OF THE INVENTION

A typical multicolor photographic element useful for optical printingcomprises a transparent support bearing a cyan dye image-forming unitcomprised of at least one red-sensitive silver halide emulsion layerhaving associated therewith at least one cyan dye-forming coupler, amagenta dye image-forming unit comprising at least one green-sensitivesilver halide emulsion layer having associated therewith at least onemagenta dye-forming coupler, and a yellow dye image-forming unitcomprising at least one blue-sensitive silver halide emulsion layerhaving associated therewith at least one, yellow dye-forming coupler.The element can contain additional layers, such as filter layers,interlayers, overcoat layers, subbing layers, and the like.

With the color negative element of the invention, the processing stepdescribed above provides a negative image. The described elements can beprocessed in the known Kodak C-41 color process as described in TheBritish Journal of Photography Annual of 1988, pages 191-198. Suchnegative working emulsions are typically sold with instructions toprocess using a color negative method such as the mentioned C-41process.

The photographic element of this invention comprises one or more of thenondiffusing cyan dyes of the formula: ##STR5## wherein: R1 is an alkoxygroup, a phenoxy group or a halogen atom;

R2 is hydrogen, an alkyl group, a phenyl group; a halogen atom, analkoxy carbonyl group of formula --COOR7, or a carbonamido group offormula --NR8COR7;

R3, R4, R5 and R8 are independently hydrogen or an alkyl group;

R6 is an alkyl group; and

R7 is an alkyl group or a phenyl group.

These dyes may be employed in any layer of the photographic element butare typically employed in non-light sensitive layers and, where it isdesired to maximize the speed of the red light sensitive layers, belowone or more of the red light sensitive layers. The dummy dye may be, forexample, in a layer adjacent to and on either the top sensitized layerside of the transparent support or on the bottom or side opposite thesensitized layers. By reference to the terms "under", "above", "below"or the like it is assumed that the element is oriented with thesensitized layers above the support so that the incident light resultingin the original image is from the top of the element.

R1 in the above formula may optionally be restricted to an unbranchedalkoxy group (which itself may be restricted to unbranched andunsubstituted alkoxy), a phenoxy group or a halogen. The cyan dummy dyemay be selected so as to not have any acid or acid salt groups present(such as --SO₃ H, --COOH or their salts). In particular, R1, R2 and R3may be selected such that they do not have an an acid or acid salt grouppresent (particularly, they do not have --SO₃ H, --COOH or their saltspresent). Alternatively, R1 may be an alkoxy group (which by thedefinition above, includes both branched and unbranched groups) while R2is an unsubstituted alkyl and R3 is hydrogen.

To produce a nondiffusable dye of low water solubility, the total numberof carbon atoms in R1, R2 and R3 taken together should be at least 8 andpreferably from 10 to 30. Suitably R4 is methyl, R5 is ethyl and R6 iseither ethyl, beta-hydroxyethyl or beta- (methylsulfonamido)ethyl, sincethen the dye may be synthesized from commonly used developing agents.

The photographic elements of this invention can have the cyan dummy dyesof the type described above, incorporated in them by first dispersing anoil phase containing the dye in an aqueous phase containing a binder,such as gelatin, and one or more surfactants. The dye-containingdispersion is then coated in the appropriate layer of a multilayer filmon a suitable support. The oil phase usually consists of the dyedissolved in one or more high-boiling solvents. This is typically addedto an aqueous solution of gelatin and surfactant, which is followed bymilling or homogenization of the mixture to disperse the oil phase inthe aqueous phase as small droplets. Removable (by washing orevaporation) auxiliary solvents, such as ethyl acetate or cyclohexanone,may also be used in the preparation of such dispersions to facilitatedissolution of the dye in the oil phase.

High-boiling solvents useful for the practice of this invention includearyl phosphates (e.g. tritolyl phosphate), alkyl phosphates (eg.trioctyl phosphate), mixed aryl alkyl phosphates (e.g. diphenyl2-ethylhexyl phosphate), aryl, alkyl or mixed aryl-alkyl phosphonates,phosphine oxides (e.g. trioctylphosphine oxide), esters of aromaticacids (e.g. dibutyl phthalate), esters of aliphatic acids (eg. dibutylsebecate), alcohols (e.g. 2-hexyl-1-decanol), phenols (e.g.p-dodecylphenol), carbonamides (e.g. N,N-dibutyldodecanamide orN-butylacetanalide), sulfoxides (e.g. bis(2-ethylhexyl)sulfoxide),sulfonamides (e.g. N,N-dibutyl-p-toluenesulfonamide) or hydrocarbons(e.g. dodecylbenzene). Additional high-boiling solvents and auxiliarysolvents are noted in the Research Disclosure references below. Usefuldye:high-boiling solvent weight ratios range from about 1:0.1 to 1:10,with 1:0.3 to 1:5.0 being preferred.

The above described cyan dummy dyes may be coated in the photographicelements of this invention together with other dyes or addenda in thesame layer or layers. In the photographic elements of this invention thecyan dyes are typically coated under at least one of the red-sensitivelayers in a multilayer film. It is most common to coat these cyan dummydyes in a layer adjacent to the transparent film support and under allof the red-sensitive layers of a multilayer film. However, the describedcyan dummy dyes may also be coated under the support on the side of thesupport opposite the side on which the light-sensitiveemulsion-containing layers are coated. In photographic elements of thepresent invention, the above described cyan dummy dyes may also beconveniently coated in one or more of the lower silver halide containingred-sensitive layers of a multilayer film containing more than onered-sensitive layer. Useful coated levels of the cyan dummy dyes of thisinvention range from about 0.002 g/sq m to 0.150 g/sq m, with coatedlevels ranging from 0.004 g/sq m to 0.050 g/sq m being typical).

To make photographic elements of the present invention, a layercontaining a cyan dummy dye of the above described type is formed.Preferably, as described above, at least one red-sensitive layer istypically formed above the cyan dummy dye containing layer, whichred-sensitive layer contains a cyan dye forming coupler which forms acyan dye upon exposure and processing of the element. In a known manner,further layers or additives may be provided in the photographic elementas described herein or which are known.

Examples of cyan dummy dyes of this invention include but are notlimited to the following (D1-D24): ##STR6##

In addition to the cyan dummy dye, a layer of the negative element alsocontains a ballasted stabilizer compound therefor. Such compound has theformula:

    B--L--A--R                                                 (II)

wherein:

B is a ballast group;

L is a divalent linking group;

A is a group of the formula: ##STR7## wherein R' is hydrogen or an alkylor alkoxy group; and

R is hydrogen or an aliphatic or aromatic group linked directly orthrough a nitrogen or oxygen atom to A.

The group B serves the purpose of ballasting the stabilizer within theelement so that it will remain in the vicinity of the dummy dye that itserves to stabilize. Ballast materials are well-known in the art asdescribed in the Research Disclosure publications hereafter. Typically,they comprise the same types of hydrophobic materials described for usewith the dyes of the invention. Conveniently, they may be polymeric innature enabling them to incorporate more than one stabilizing group permolecule.

Generally, B is a group containing at least 6 carbon atoms. Suitably Bis a polymer having backbone molecular weight of greater than 1000 whichmay comprise a polyvinyl, polyester, polyether, polyurethane, polyamide,polyacrylate, or polymethacrylate polymer or copolymers thereof. It isespecially suitable when the polymeric chain is a polyalkylene group,especially one obtained by polymerizing an acrylate or methacrylatemonomer.

In formula (III), L is a divalent linking group. There are no particularlimitations as to the identity of the linking group so long as it doesnot interfere through reactivity or otherwise with the intendedphotographic function of the element. Thus the group may be methylene,or a chain containing one or more alkylene or arylene groups possiblyinterrupted by heteroatoms such as oxygen or nitrogen.

Desirably, L contains and is linked to B by a group such as --C(O)O--,--C(O)NR'--, --CH₂ --, --O--, --NR'--, --OR'--, --OR'O--, --C(O)OR'O--,--C(O)R'O--, or --C(O)N(R')R"O-- wherein each R' is independentlyhydrogen or an alkyl group and each R" is an independently selectedalkyl group. Suitable examples are --C(O)OCH₂ CH₂ O--, --C(O)OCH₂ CH₂CH₂ O--, --C(O)NHCH₂ CH₂ CH₂ NH--, --C(O)OCH₂ CH₂ NH--, --C(O)OCH₂C(CH₃)₂ --, --C(O)OCH₂ C(CH₃)₂ CH₂ O--, --C(O)NHCH₂ CH₂ O--, and--C(O)OCH₂ CH(CH₃)O--.

A is a group of the formula: ##STR8## wherein R' is hydrogen or an alkylor alkoxy group. Most typically, R' is hydrogen or lower alkyl such asmethyl.

R is hydrogen or an aliphatic or aromatic group linked directly orthrough a nitrogen or oxygen atom to A. R is typically an alkyl, aryl,alkoxy, aryloxy, alkylamido, or arylamido group. An alkyl group,particularly an unsubstituted alkyl group such as methyl or ethyl aresatisfactory and readily manufactured.

In the case of a polymeric B group, synthesis methods are well-known.For example, in latex polymerization, the selected monomers arecolloidally emulsified in an aqueous medium that usually contains acationic, nonionic, or zwiterionic surfactant and a polymerizationcatalyst such as 2,2'-azobis(2-amidinopropane)hydrochloride. Theresulting colloidal emulsion is then subjected to conditions conduciveto polymerization of the monomeric species to produce an aqueouscolloidal dispersion commonly called a latex. General methods forpreparation may be found in Principles of Polymerization 2d Ed, G.Odian, J. Wiley, N.Y., NY (1981).

The following are examples of compounds which may suitably be used asstabilizers of the invention: ##STR9##

Suitable repeating units useful when B is a polymer are (at >1 wt % inpolymer): ##STR10##

Unless otherwise specifically stated, substituent groups which may besubstituted on molecules herein include any groups, whether substitutedor unsubstituted, which do not destroy properties necessary forphotographic utility. When the term "group" is applied to theidentification of a substituent containing a substitutable hydrogen, itis intended to encompass not only the substituent's unsubstituted form,but also its form further substituted with any group or groups as hereinmentioned. Suitably, the group may be halogen or may be bonded to theremainder of the molecule by an atom of carbon, silicon, oxygen,nitrogen, phosphorous, or sulfur. The substituent may be, for example,halogen, such as chlorine, bromine or fluorine; nitro; hydroxyl; cyano;carboxyl; or groups which may be further substituted, such as alkyl,including straight or branched chain alkyl, such as methyl,trifluoromethyl, ethyl, t-butyl, 3-(2,4-di-t-pentylphenoxy) propyl, andtetradecyl; alkenyl, such as ethylene, 2-butene; alkoxy, such asmethoxy, ethoxy, propoxy, butoxy, 2-methoxyethoxy, sec-butoxy, hexyloxy,2-ethylhexyloxy, tetradecyloxy, 2-(2,4-di-t-pentylphenoxy)ethoxy, and2-dodecyloxyethoxy; aryl such as phenyl, 4-t-butylphenyl,2,4,6-trimethylphenyl, naphthyl; aryloxy, such as phenoxy,2-methylphenoxy, alpha-or beta-naphthyloxy, and 4-tolyloxy; carbonamido,such as acetamido, benzamido, butyramido, tetradecanamido,alpha-(2,4-di-t-pentyl-phenoxy)acetamido,alpha-(2,4-di-t-pentylphenoxy)butyramido,alpha-(3-pentadecylphenoxy)-hexanamido,alpha-(4-hydroxy-3-t-butylphenoxy)-tetradecanamido,2-oxo-pyrrolidin-1-yl, 2-oxo-5-tetradecylpyrrolin-1-yl,N-methyltetradecanamido, N-succinimido, N-phthalimido,2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-imidazolyl, andN-acetyl-N-dodecylamino, ethoxycarbonylamino, phenoxycarbonylamino,benzyloxycarbonylamino, hexadecyloxycarbonylamino,2,4-di-t-butylphenoxycarbonylamino, phenylcarbonylamino,2,5-(di-t-pentylphenyl)carbonylamino, p-dodecyl-phenylcarbonylamino,p-toluylcarbonylamino, N-methylureido, N,N-dimethylureido,N-methyl-N-dodecylureido, N-hexadecylureido, N,N-dioctadecylureido,N,N-dioctyl-N'-ethylureido, N-phenylureido, N,N-diphenylureido,N-phenyl-N-p-toluylureido, N-(m-hexadecylphenyl)ureido,N,N-(2,5-di-t-pentylphenyl)-N'-ethylureido, and t-butylcarbonamido;sulfonamido, such as methylsulfonamido, benzenesulfonamido,p-toluylsulfonamido, p-dodecylbenzenesulfonamido,N-methyltetradecylsulfonamido, N,N-dipropyl-sulfamoylamino, andhexadecylsulfonamido; sulfamoyl, such as N-methylsulfamoyl,N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-hexadecylsulfamoyl,N,N-dimethylsulfamoyl; N- 3-(dodecyloxy)propyl!sulfamoyl, N-4-(2,4-di-t-pentylphenoxy)butyl!sulfamoyl,N-methyl-N-tetradecylsulfamoyl, and N-dodecylsulfamoyl; carbamoyl, suchas N-methylcarbamoyl, N,N-dibutylcarbamoyl, N-octadecylcarbamoyl, N-4-(2,4-di-t-pentylphenoxy)butyl!carbamoyl,N-methyl-N-tetradecylcarbamoyl, and N,N-dioctylcarbamoyl; acyl, such asacetyl, (2,4-di-t-amylphenoxy)acetyl, phenoxycarbonyl,p-dodecyloxyphenoxycarbonyl methoxycarbonyl, butoxycarbonyl,tetradecyloxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl,3-pentadecyloxycarbonyl, and dodecyloxycarbonyl; sulfonyl, such asmethoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl,2-ethylhexyloxysulfonyl, phenoxysulfonyl,2,4-di-t-pentylphenoxysulfonyl, methylsulfonyl, octylsulfonyl,2-ethylhexylsulfonyl, dodecylsulfonyl, hexadecylsulfonyl,phenylsulfonyl, 4-nonylphenylsulfonyl, and p-toluylsulfonyl;sulfonyloxy, such as dodecylsulfonyloxy, and hexadecylsulfonyloxy;sulfinyl, such as methylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl,dodecylsulfinyl, hexadecylsulfinyl, phenylsulfinyl,4-nonylphenylsulfinyl, and p-toluylsulfinyl; thio, such as ethylthio,octylthio, benzylthio, tetradecylthio,2-(2,4-di-t-pentylphenoxy)ethylthio, phenylthio,2-butoxy-5-t-octylphenylthio, and p-tolylthio; acyloxy, such asacetyloxy, benzoyloxy, octadecanoyloxy, p-dodecylamidobenzoyloxy,N-phenylcarbamoyloxy, N-ethylcarbamoyloxy, and cyclohexylcarbonyloxy;amine, such as phenylanilino, 2-chloroanilino, diethylamine,dodecylamine; imino, such as 1 (N-phenylimido)ethyl, N-succinimido or3-benzylhydantoinyl; phosphate, such as dimethylphosphate andethylbutylphosphate; phosphite, such as diethyl and dihexylphosphite; aheterocyclic group, a heterocyclic oxy group or a heterocyclic thiogroup, each of which may be substituted and which contain a 3 to 7membered heterocyclic ring composed of carbon atoms and at least onehetero atom selected from the group consisting of oxygen, nitrogen andsulfur, such as 2-furyl, 2-thienyl, 2-benzimidazolyloxy or2-benzothiazolyl; quaternary ammonium, such as triethylammonium; andsilyloxy, such as trimethylsilyloxy.

If desired, the substituents may themselves be further substituted oneor more times with the described substituent groups. The particularsubstituents used may be selected by those skilled in the art to attainthe desired photographic properties for a specific application and caninclude, for example, hydrophobic groups, solubilizing groups, blockinggroups, releasing or releasable groups, etc. Generally, the above groupsand substituents thereof may include those having up to 48 carbon atoms,typically 1 to 36 carbon atoms and usually less than 24 carbon atoms,but greater numbers are possible depending on the particularsubstituents selected.

To control the migration of various components, it may be desirable toinclude a high molecular weight hydrophobe or "ballast" group in couplermolecules and in the stabilizer of the invention. Representative ballastgroups include substituted or unsubstituted alkyl or aryl groupscontaining 8 to 48 carbon atoms. Representative substituents on suchgroups include alkyl, aryl, alkoxy, aryloxy, alkylthio, hydroxy,halogen, alkoxycarbonyl, aryloxcarbonyl, carboxy, acyl, acyloxy, amino,anilino, carbonamido, carbamoyl, alkylsulfonyl, arylsulfonyl,sulfonamido, and sulfamoyl groups wherein the substituents typicallycontain 1 to 42 carbon atoms. Such substituents can also be furthersubstituted.

If desired, the photographic element can be used in conjunction with anapplied magnetic layer as described in Research Disclosure, November1992, Item 34390 published by Kenneth Mason Publications, Ltd., DudleyAnnex, 12a North Street, Emsworth, Hampshire P010 7DQ, ENGLAND, and asdescribed in Hatsumi Kyoukai Koukai Gihou No. 94-6023, published Mar.15, 1994, avaliable from the Japanese Patent Office, the contents ofwhich are incorporated herein by reference. When it is desired to employthe inventive materials in a small format film, Research Disclosure,June 1994, Item 36230, provides suitable embodiments.

In the following discussion of suitable materials for use in theemulsions and elements of this invention, reference will be made toResearch Disclosure, September 1994, Item 36544, available as describedabove, which will be identified hereafter by the term "ResearchDisclosure" The contents of the Research Disclosure, including thepatents and publications referenced therein, are incorporated herein byreference, and the Sections hereafter referred to are Sections of theResearch Disclosure.

Except as provided, the silver halide emulsion containing elementsemployed in this invention can be either negative-working orpositive-working as indicated by the type of processing instructions(i.e. color negative, reversal, or direct positive processing) providedwith the element. Suitable emulsions and their preparation as well asmethods of chemical and spectral sensitization are described in SectionsI through V. Various additives such as UV dyes, brighteners,antifoggants, stabilizers, light absorbing and scattering materials, andphysical property modifying addenda such as hardeners, coating aids,plasticizers, lubricants and matting agents are described, for example,in Sections II and VI through VIII. Color materials are described inSections X through XIII. Scan facilitating is described in Section XIV.Supports, exposure, development systems, and processing methods andagents are described in Sections XV to XX. Certain desirablephotographic elements and processing steps, particularly those useful inconjunction with color reflective prints, are described in ResearchDisclosure, Item 37038, February. 1995.

Coupling-off groups are well known in the art. Such groups can determinethe chemical equivalency of a coupler, i.e., whether it is a2-equivalent or a 4-equivalent coupler, or modify the reactivity of thecoupler. Such groups can advantageously affect the layer in which thecoupler is coated, or other layers in the photographic recordingmaterial, by performing, after release from the coupler, functions suchas dye formation, dye hue adjustment, development acceleration orinhibition, bleach acceleration or inhibition, electron transferfacilitation, color correction and the like.

The presence of hydrogen at the coupling site provides a 4-equivalentcoupler, and the presence of a coupling-off group usually provides a2-equivalent coupler. Representative classes of such coupling-off groupsinclude, for example, chloro, alkoxy, aryloxy, hetero-oxy, sulfonyloxy,acyloxy, acyl, heterocyclyl, sulfonamido, mercaptotetrazole,benzothiazole, mercaptopropionic acid, phosphonyloxy, arylthio, andarylazo. These coupling-off groups are described in the art, forexample, in U.S. Pat. Nos. 2,455,169, 3,227,551, 3,432,521, 3,476,563,3,617,291, 3,880,661, 4,052,212 and 4,134,766; and in UK. Patents andpublished application Nos. 1,466,728, 1,531,927, 1,533,039, 2,006,755Aand 2,017,704A, the disclosures of which are incorporated herein byreference.

Image dye-forming couplers may be included in the element such ascouplers that form cyan dyes upon reaction with oxidized colordeveloping agents which are described in such representative patents andpublications as: U.S. Pat. Nos. 2,367,531, 2,423,730, 2,474,293,2,772,162, 2,895,826, 3,002,836, 3,034,892, 3,041,236, 4,333,999,4,883,746 and "Farbkuppler-eine Literature Ubersicht," published in AgfaMitteilungen, Band III, pp. 156-175 (1961). Preferably such couplers arephenols and naphthols that form cyan dyes on reaction with oxidizedcolor developing agent.

Couplers that form magenta dyes upon reaction with oxidized colordeveloping agent are described in such representative patents andpublications as: U.S. Pat. Nos. 2,311,082, 2,343,703, 2,369,489,2,600,788, 2,908,573, 3,062,653, 3,152,896, 3,519,429, 3,758,309,4,540,654, and "Farbkuppler-eine Literature Ubersicht," published inAgfa Mitteilungen, Band III, pp. 126-156 (1961). Preferably suchcouplers are pyrazolones, pyrazolotriazoles, or pyrazolobenzimidazolesthat form magenta dyes upon reaction with oxidized color developingagents.

Couplers that form yellow dyes upon reaction with oxidized colordeveloping agent are described in such representative patents andpublications as: U.S. Pat. Nos. 2,298,443, 2,407,210, 2,875,057,3,048,194, 3,265,506, 3,447,928, 4,022,620, 4,443,536, and"Farbkuppler-eine Literature Ubersicht," published in Agfa Mitteilungen,Band III, pp. 112-126 (1961). Such couplers are typically open chainketomethylene compounds.

Couplers that form colorless products upon reaction with oxidized colordeveloping agent are described in such representative patents as: UK.Patent No. 861,138; U.S. Pat. Nos. 3,632,345, 3,928,041, 3,958,993 and3,961,959. Typically such couplers are cyclic carbonyl containingcompounds that form colorless products on reaction with an oxidizedcolor developing agent.

Couplers that form black dyes upon reaction with oxidized colordeveloping agent are described in such representative patents as U.S.Pat. Nos. 1,939,231; 2,181,944; 2,333,106; and 4,126,461; German OLS No.2,644,194 and German OLS No. 2,650,764. Typically, such couplers areresorcinols or m-aminophenols that form black or neutral products onreaction with oxidized color developing agent.

In addition to the foregoing, so-called "universal" or "washout"couplers may be employed. These couplers do not contribute to imagedye-formation. Thus, for example, a naphthol having an unsubstitutedcarbamoyl or one substituted with a low molecular weight substituent atthe 2-or 3-position may be employed. Couplers of this type aredescribed, for example, in U.S. Pat. Nos. 5,026,628, 5,151,343, and5,234,800.

It may be useful to use a combination of couplers any of which maycontain known ballasts or coupling-off groups such as those described inU.S. Pat. No. 4,301,235; U.S. Pat. No. 4,853,319 and U.S. Pat. No.4,351,897. The coupler may contain solubilizing groups such as describedin U.S. Pat. No. 4,482,629. The coupler may also be used in associationwith "wrong" colored couplers (e.g. to adjust levels of interlayercorrection) and, in color negative applications, with masking couplerssuch as those described in EP 213.490; Japanese Published Application58-172,647; U.S. Pat. Nos. 2,983,608; 4,070,191; and 4,273,861; GermanApplications DE 2,706,117 and DE 2,643,965; UK. Patent 1,530,272; andJapanese Application 58-113935. The masking couplers may be shifted orblocked, if desired.

The invention materials may be used in association with materials thataccelerate or otherwise modify the processing steps e.g. of bleaching orfixing to improve the quality of the image. Bleach accelerator releasingcouplers such as those described in EP 193,389; EP 301,477; U.S. Pat.No. 4,163,669; U.S. Pat. No. 4,865,956; and U.S. Pat. No. 4,923,784, maybe useful. Also contemplated is use of the compositions in associationwith nucleating agents, development accelerators or their precursors (UKPatent 2,097,140; UK. Patent 2,131,188); electron transfer agents (U.S.Pat. No. 4,859,578; U.S. Pat. No. 4,912,025); antifogging and anticolor-mixing agents such as derivatives of hydroquinones, aminophenols,amines, gallic acid; catechol; ascorbic acid; hydrazides;sulfonamidophenols; and non color-forming couplers.

The invention materials may also be used in combination with filter dyelayers comprising colloidal silver sol or yellow, cyan, and/or magentafilter dyes, either as oil-in-water dispersions, latex dispersions or assolid particle dispersions. Additionally, they may be used with"smearing" couplers (e.g. as described in U.S. Pat. No. 4,366,237; EP96,570; U.S. Pat. No. 4,420,556; and U.S. Pat. No. 4,543,323.) Also, thecompositions may be blocked or coated in protected form as described,for example, in Japanese Application 61/258,249 or U.S. Pat. No.5,019,492.

The invention materials may further be used in combination withimage-modifying compounds such as "Developer Inhibitor-Releasing"compounds (DIR's). DIR's useful in conjunction with the compositions ofthe invention are known in the art and examples are described in U.S.Pat. Nos. 3,137,578; 3,148,022; 3,148,062; 3,227,554; 3,384,657;3,379,529; 3,615,506; 3,617,291; 3,620,746; 3,701,783; 3,733,201;4,049,455; 4,095,984; 4,126,459; 4,149,886; 4,150,228; 4,211,562;4,248,962; 4,259,437; 4,362,878; 4,409,323; 4,477,563; 4,782,012;4,962,018; 4,500,634; 4,579,816; 4,607,004; 4,618,571; 4,678,739;4,746,600; 4,746,601; 4,791,049; 4,857,447; 4,865,959; 4,880,342;4,886,736; 4,937,179; 4,946,767; 4,948,716; 4,952,485; 4,956,269;4,959,299; 4,966,835; 4,985,336 as well as in patent publications GB1,560,240; GB 2,007,662; GB 2,032,914; GB 2,099,167; DE 2,842,063, DE2,937,127; DE 3,636,824; DE 3,644,416 as well as the following EuropeanPatent Publications: 272,573; 335,319; 336,411; 346, 899; 362, 870;365,252; 365,346; 373,382; 376,212; 377,463; 378,236; 384,670; 396,486;401,612; 401,613.

Such compounds are also disclosed in "Developer-Inhibitor-Releasing(DIR) Couplers for Color Photography," C. R. Barr, J. R. Thirtle and P.W. Vittum in Photographic Science and Engineering, Vol. 13, p. 174(1969), incorporated herein by reference. Generally, the developerinhibitor-releasing (DIR) couplers include a coupler moiety and aninhibitor coupling-off moiety (IN). The inhibitor-releasing couplers maybe of the time-delayed type (DIAR couplers) which also include a timingmoiety or chemical switch which produces a delayed release of inhibitor.Examples of typical inhibitor moieties are: oxazoles, thiazoles,diazoles, triazoles, oxadiazoles, thiadiazoles, oxathiazoles,thiatriazoles, benzotriazoles, tetrazoles, benzimidazoles, indazoles,isoindazoles, mercaptotetrazoles, selenotetrazoles,mercaptobenzothiazoles, selenobenzothiazoles, mercaptobenzoxazoles,selenobenzoxazoles, mercaptobenzimidazoles, selenobenzimidazoles,benzodiazoles, mercaptooxazoles, mercaptothiadiazoles,mercaptothiazoles, mercaptotriazoles, mercaptooxadiazoles,mercaptodiazoles, mercaptooxathiazoles, telleurotetrazoles orbenzisodiazoles. In a preferred embodiment, the inhibitor moiety orgroup is selected from the following formulas: ##STR11## wherein R_(I)is selected from the group consisting of straight and branched alkyls offrom 1 to about 8 carbon atoms, benzyl, phenyl, and alkoxy groups andsuch groups containing none, one or more than one such substituent;

R_(II) is selected from R_(I) and --SR_(I) ; R_(III) is a straight orbranched alkyl group of from 1 to about 5 carbon atoms and m is from 1to 3; and

R_(IV) is selected from the group consisting of hydrogen, halogens andalkoxy, phenyl and carbonamido groups, --COOR_(V) and --NHCOOR_(V)wherein R_(V) is selected from substituted and unsubstituted alkyl andaryl groups.

Although it is typical that the coupler moiety included in the developerinhibitor-releasing coupler forms an image dye corresponding to thelayer in which it is located, it may also form a different color as oneassociated with a different film layer. It may also be useful that thecoupler moiety included in the developer inhibitor-releasing couplerforms colorless products and/or products that wash out of thephotographic material during processing (so-called "universal"couplers).

As mentioned, the developer inhibitor-releasing coupler may include atiming group, which produces the time-delayed release of the inhibitorgroup such as groups utilizing the cleavage reaction of a hemiacetal(U.S. Pat. No. 4,146,396, Japanese Applications 60-249148; 60-249149);groups using an intramolecular nucleophilic substitution reaction (U.S.Pat. No. 4,248,962); groups utilizing an electron transfer reactionalong a conjugated system (U.S. Pat. No. 4,409,323; 4,421,845; JapaneseApplications 57-188035; 58-98728; 58-209736; 58-209738) groups utilizingester hydrolysis (German Patent Application (OLS) No. 2,626,315); groupsutilizing the cleavage of imino ketals (U.S. Pat. No. 4,546,073); groupsthat function as a coupler or reducing agent after the coupler reaction(U.S. Pat. No. 4,438,193; U.S. Pat. No. 4,618,571) and groups thatcombine the features describe above. It is typical that the timing groupor moiety is of one of the formulas: ##STR12## wherein IN is theinhibitor moiety, Z is selected from the group consisting of nitro,cyano, alkylsulfonyl; sulfamoyl (--SO₂ NR₂); and sulfonamido (--NRSO₂ R)groups; n is 0 or 1; and R_(VI) is selected from the group consisting ofsubstituted and unsubstituted alkyl and phenyl groups. The oxygen atomof each timing group is bonded to the coupling-off position of therespective coupler moiety of the DIAR.

Suitable developer inhibitor-releasing couplers for use in the presentinvention include, but are not limited to, the following: ##STR13##

It is also contemplated that the concepts of the present invention maybe employed to obtain reflection color prints as described in ResearchDisclosure, November 1979, Item 18716, available from Kenneth MasonPublications, Ltd, Dudley Annex, 12a North Street, Emsworth, HampshireP0101 7DQ, England, incorporated herein by reference. Materials of theinvention may be coated on pH adjusted support as described in U.S. Pat.No. 4,917,994; on a support with reduced oxygen permeability (EP553,339); with epoxy solvents (EP 164,961); with nickel complexstabilizers (U.S. Pat. No. 4,346,165; U.S. Pat. No. 4,540,653 and U.S.Pat. No. 4,906,559 for example); with ballasted chelating agents such asthose in U.S. Pat. No. 4,994,359 to reduce sensitivity to polyvalentcations such as calcium; and with stain reducing compounds such asdescribed in U.S. Pat. No. 5,068,171. Other compounds useful incombination with the invention are disclosed in Japanese PublishedApplications described in Derwent Abstracts having accession numbers asfollows: 90-072,629, 90-072,630; 90-072,631; 90-072,632; 90-072,633;90-072,634; 90-077,822; 90-078,229; 90-078,230; 90-079,336; 90-079,337;90-079,338; 90-079,690; 90-079,691; 90-080,487; 90-080,488; 90-080,489;90-080,490; 90-080,491; 90-080,492; 90-080,494; 90-085,928; 90-086,669;90-086,670; 90-087,360; 90-087,361; 90-087,362; 90-087,363; 90-087,364;90-088,097; 90-093,662; 90-093,663; 90-093,664; 90-093,665; 90-093,666;90-093,668; 90-094,055; 90-094,056; 90-103,409; 83-62,586; 83-09,959.

Especially useful in this invention are tabular grain silver halideemulsions. Specifically contemplated tabular grain emulsions are thosein which greater than 50 percent of the total projected area of theemulsion grains are accounted for by tabular grains having a thicknessof less than 0.3 micron (0.5 micron for blue sensitive emulsion) and anaverage tabularity (T) of greater than 25 (preferably greater than 100),where the term "tabularity" is employed in its art recognized usage as

    T=ECD/t.sup.2

where

ECD is the average equivalent circular diameter of the tabular grains inmicrometers and

t is the average thickness in micrometers of the tabular grains.

The average useful ECD of photographic emulsions can range up to about10 micrometers, although in practice emulsion ECD's seldom exceed about4 micrometers. Since both photographic speed and granularity increasewith increasing ECD's, it is generally preferred to employ the smallesttabular grain ECD's compatible with achieving aim speed requirements.

Emulsion tabularity increases markedly with reductions in tabular grainthickness. It is generally preferred that aim tabular grain projectedareas be satisfied by thin (t<0.2 micrometer) tabular grains. To achievethe lowest levels of granularity it is preferred that aim tabular grainprojected areas be satisfied with ultrathin (t<0.06 micrometer) tabulargrains. Tabular grain thicknesses typically range down to about 0.02micrometer. However, still lower tabular grain thicknesses arecontemplated. For example, Daubendiek et al U.S. Pat. No. 4,672,027reports a 3 mole percent iodide tabular grain silver bromoiodideemulsion having a grain thickness of 0.017 micrometer. Ultrathin tabulargrain high chloride emulsions are disclosed by Maskasky U.S. Pat. No.5,217,858.

As noted above tabular grains of less than the specified thicknessaccount for at least 50 percent of the total grain projected area of theemulsion. To maximize the advantages of high tabularity it is generallypreferred that tabular grains satisfying the stated thickness criterionaccount for the highest conveniently attainable percentage of the totalgrain projected area of the emulsion. For example, in preferredemulsions, tabular grains satisfying the stated thickness criteria aboveaccount for at least 70 percent of the total grain projected area. Inthe highest performance tabular grain emulsions, tabular grainssatisfying the thickness criteria above account for at least 90 percentof total grain projected area.

Suitable tabular grain emulsions can be selected from among a variety ofconventional teachings, such as those of the following: ResearchDisclosure, Item 22534, January 1983, published by Kenneth MasonPublications, Ltd., Emsworth, Hampshire P010 7DD, England; U.S. Pat.Nos. 4,439,520; 4,414,310; 4,433,048; 4,643,966; 4,647,528; 4,665,012;4,672,027; 4,678,745; 4,693,964; 4,713,320; 4,722,886; 4,755,456;4,775,617; 4,797,354; 4,801,522; 4,806,461; 4,835,095; 4,853,322;4,914,014; 4,962,015; 4,985,350; 5,061,069 and 5,061,616.

The emulsions can be surface-sensitive emulsions, i.e., emulsions thatform latent images primarily on the surfaces of the silver halidegrains, or the emulsions can form internal latent images predominantlyin the interior of the silver halide grains. The emulsions can benegative-working emulsions, such as surface-sensitive emulsions orunfogged internal latent image-forming emulsions, or direct-positiveemulsions of the unfogged, internal latent image-forming type, which arepositive-working when development is conducted with uniform lightexposure or in the presence of a nucleating agent.

Photographic elements can be exposed to actinic radiation, typically inthe visible region of the spectrum, to form a latent image and can thenbe processed to form a visible dye image. Processing to form a visibledye image includes the step of contacting the element with a colordeveloping agent to reduce developable silver halide and oxidize thecolor developing agent. Oxidized color developing agent in turn reactswith the coupler to yield a dye.

Preferred color developing agents are p-phenylenediamines such as:

4-amino-N,N-diethylaniline hydrochloride,

4-amino-3-methyl-N,N-diethylaniline hydrochloride,

4-amino-3-methyl-N-ethyl-N-(2-methanesulfonamido-ethyl)anilinesesquisulfate hydrate,

4-amino-3-methyl-N-ethyl-N-(2-hydroxyethyl)aniline sulfate,

4-amino-3-(2-methanesulfonamido-ethyl)-N,N-diethylaniline hydrochlorideand

4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene sulfonicacid.

Development is usually followed by the conventional steps of bleaching,fixing, or bleach-fixing, to remove silver or silver halide, washing,and drying.

EXAMPLE 1

To a glow-discharge-treated polyethylene-2,6-naphthalene support, whichwas coated with a continuous subbing layer consisting of a terpolymer ofn-butyl acryate, 2-aminoethyl methacrylate hydrochloride, and2-hydroxyethyl methacrylate (50:05:45 wt ratio), gelatin, andsurfactant; the following layers were applied in the indicated sequenceto produce Coating 4-1. The quantities quoted each relate to g/m².Emulsion sizes as determined by the disc centrifuge method are reportedin Diameter×Thickness in microns. The emulsions in the cyan layers aresensitized with dye set 1. The emulsions in the magenta layers aresensitized with dye set 2. The emulsions in the yellow layers aresensitized with sensitizing dye YD-A.

    ______________________________________                                        Layer 1                                                                              Antilialation Undercoat                                                       Black colloidal silver    0.15                                                Gelatin                   1.61                                                Hexasodium salt of metaphosphoric acid                                                                  0.011                                               Disodium salt of 3,5,-disulfocatecol                                                                    0.270                                               4-4-phenyl disulfide diacetanilide                                                                      0.0012                                              Dye 1                     0.014                                               Dye 2 (D-2)               0.022                                               Oxidized developer scavenger O-2                                                                        0.14                                                Dye 5                     0.016                                               4-carboxymethyl-4-thiazolone-2-thione                                                                   0.0009                                       Layer 3                                                                              Slow cyan layer                                                               Tabular emulsion, 1.1 × .09, 4.1 mole % I                                                         0.27                                                Tabular emulsion, 0.5 × .08, 1.3 mole % I                                                         0.47                                                Gelatin                   2.01                                                Cyan dye forming coupler C-1                                                                            0.48                                                Bleach accelerator releasing coupler B-2                                                                0.082                                               Masking Coupler MC-1      0.028                                        Layer 4                                                                              Mid cyan layer                                                                Tabular emulsion, 1.3 × .12, 4.1 mole % I                                                         0.79                                                Gelatin                   1.18                                                Cyan dye forming coupler C-1                                                                            0.16                                                Development inhibitor releasing coupler DIR-1                                                           0.011                                               Masking Coupler MC-1      0.022                                        Layer 5                                                                              Fast cyan layer                                                               Tabular emulsion, 2.5 × .12, 4.1 mole % I                                                         1.076                                               Gelatin                   1.24                                                Cyan dye forming coupler C-1                                                                            0.12                                                Development inhibitor releasing coupler DIR-1                                                           0.019                                               Development inhibitor releasing coupler DIR-2                                                           0.048                                               Masking Coupler MC-1      0.032                                        Layer 6                                                                              Interlayer                                                                    Gelatin                   0.70                                                Oxidized developer scavenger O-2                                                                        0.075                                        Layer 7                                                                              Yellow magenta layer                                                          Tabular emulsion, 1.0 × .09, 4.1 mole % I                                                         0.24                                                Tabular emulsion, 0.5 × .08, 1.3 mole % I                                                         0.51                                                Gelatin                   1.18                                                Magenta dye forming coupler M-1                                                                         0.30                                                Masking Coupler MC-2      0.042                                        Layer 8                                                                              Mid magenta layer                                                             Tabular emulsion, 1.3 × .12, 4.1 mole % I                                                         0.97                                                Gelatin                   1.32                                                Development inhibitor releasing coupler DIR-3                                                           0.024                                               Magenta dye forming coupler M-1                                                                         0.057                                               Masking Coupler MC-2      0.032                                        Layer 9                                                                              Fast magenta layer                                                            Tabular emulsion, 2.3 × .12, 4.1 mole % I                                                         0.97                                                Gelatin                   1.55                                                Development inhibitor releasing coupler DIR-4                                                           0.011                                               Development inhibitor releasing coupler DIR-5                                                           0.011                                               Magenta dye forming coupler M-1                                                                         0.088                                               Masking Coupler MC-2      0.043                                        Layer 10                                                                             Yellow filter layer                                                           Yellow filter dye AD-1    0.16                                                Gelatin                   0.65                                                Oxidized developer scavenger O-2                                                                        0.075                                        Layer 11                                                                             Slow yellow layer                                                             Tabular emulsion, 1.7 × .13, 4.1 mole % I                                                         0.23                                                Tabular emulsion, 1.1 × .13, 1.5 mole % I                                                         0.089                                               Tabular emulsion, 0.5 × .08, 1.3 mole % I                                                         0.19                                                Gelatin                   1.72                                                Yellow dye forming coupler Y-3                                                                          0.69                                                Development inhibitor releasing coupler DIR-7                                                           0.022                                               Bleach accelerator releasing coupler B-2                                                                0.002                                        Layer 12                                                                             Fast yellow layer                                                             Tabular emulsion, 3.3 × .14, 4.1 mole % I                                                         0.48                                                Gelatin                   1.38                                                Yellow dye forming coupler Y-3                                                                          0.53                                                Development inhibitor releasing coupler DIR-7                                                           0.034                                               Bleach accelerator releasing coupler B-2                                                                0.006                                               Cyan dye forming coupler C-1                                                                            0.022                                        Layer 13                                                                             UV filter layer                                                               Silver bromide Lippmann emulsion                                                                        0.215                                               UV-1                      0.108                                               UV-2                      0.108                                               Gelatin                   0.699                                        Layer 14                                                                             Protective overcoat layer                                                     Matte Beads                                                                   Gelatin                   0.882                                        ______________________________________                                    

Hardener(bis(vinylsulfonyl)methane at 1.55% of total gelatin weight).Unless otherwise noted, antifoggants (including4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene), surfactants, coating aids,emulsion addenda, sequestrants, lubricants, matte, coupler solvents, andtinting dyes were added to the appropriate layers as is common in theart. Magnetic recording layers were coated on the backside of thesupport.

Coating 1-2 was prepared like coating 1-1 except that to layer 1 wasadded 0.65 g/m² of 1,3-butanediol.

Coating 1-3 was prepared like coating 1-2 except that in layer 1 Dye 2(D-2) was omitted.

Coating 1-4 was prepared like coating 1-2 except that to layer 1 wasadded 0.65 g/m² of I-1.

Coating 1-5 was prepared like coating 1-2 except that to layer 1 wasadded 0.65 g/m² of CSt-1.

Coating 1-6 was prepared like coating 1-2 except that to layer 1 wasadded 0.65 g/m² of CSt-2.

Coating 1-7 was prepared like coating 1-2 except that to layer 1 wasadded 0.65 g/m² of I-2.

Coating 1-8 was prepared like coating 1-1 except that to layer 1 wasadded 0.65 g/m² of I-2.

Coating 1-9 was prepared like coating 1-3 except that to layer 1 wasadded 0.65 g/m² of I-2.

Coating 1-10 was prepared like coating 1-2.

Coating 1-11 was prepared like coating 1-2 except that the support wascellulose triacetate, and the hardener was coated at 1.80% of totalgelatin weight. The magnetic layers were omitted from the backside ofthe support.

Coating 1-12 was prepared like coating 1-13 except that to layer 1 wasadded 0.65 g/m² of I-2.

The results are shown in Table I.

                  TABLE I                                                         ______________________________________                                                        Delta      Delta    Delta                                                     Red Dmin   Red Dmin Red Dmin                                                  4 wk/49° C.                                                                       12 wk/26° C.                                                                    12 wk/26° C.                       Coating         minus      minus    minus                                     #     Type      4 wk/-18° C.                                                                      12 wk/-18° C.                                                                   fresh                                     ______________________________________                                        1-1   Comparative                                                                             +.057      -.005    +.005                                     1-2   Comparative                                                                             +.086      +.007    +.008                                     1-3   Comparative                                                                             +.050      +.001    .00                                       1-4   Invention +.073      -.014    .00                                       1-5   Comparative                                                                             +.086      +.003    .00                                       1-6   Comparative                                                                             +.081      -.003    +.003                                     1-7   Invention +.043      -.015    .00                                       1-8   Invention +.027      -.011    -.009                                     1-9   Comparative                                                                             +.053      +.007    +.013                                      1-10 Comparative                                                                             +.093      +.006    +.007                                      1-11 Comparative                                                                             +.052      +.012    +.023                                      1-12 Invention +.007      -.011    +.007                                     ______________________________________                                         Red Dmin = Cyan Density im area of minimum red light exposure.                4 wk/49° C. = Stored 4 weeks at 49° C. at 50% relative          humidity.                                                                     4 wk/-18° C. = Stored 4 weeks at -18° C. at 50% relative        humidity.                                                                     12 wk/26° C. = Stored 12 weeks at 26° C. at 50% relative        humidity.                                                                     12 wk/-18° C. = Stored 12 weeks at -18° C. at 50% reiative      humidity.                                                                     fresh = Stored less than one week at room temperature and humidity.      

The comparisons against a zero degree check are indications of a filmssensitivity to storage under room or other elevated temperatures.

The comparisons against a fresh check are indications of a film'sstability during storage at the indicated temperature and itssensitivity to ambient radiation.

Coating 1-1 features the use of Dye-2 (D-2) in layer 1, and demonstrateshigh red Dmin growth with 49° C. conditioning. Coating 1-2 is likecoating 1-1 except for the addition of a humectant for acceleratedhardening and for improved uniformity of hardness throughout aproduction coating roll. Coating 1-2 demonstrates even higher red Dmingrowth than coating 1-1 with 49° C. conditioning. Coating 1-3 is likecoating 1-2 except that Dye-2 was omitted. Comparing 1-3 to 1-2, onefinds that Dye-2 exacerbates red Dmin growth with 49° C. conditioning,which illustrates the problem to be solved by this invention. Coating1-4 was prepared like coating 1-2 except that to layer 1 was added 0.65g/m² of inventive stabilizer I-1, which provides lower red Dmin growthwith 49° C. or 26° C. conditioning. The level of I-1 provided enoughDmin reduction to compensate for increased Dmin due to ambientradiation, as indicated by the `Delta Red Dmin 12 wk/26° C. minus fresh`data. Coating 1-5 was prepared like coating 1-2 except that to layer 1was added 0.65 g/m² of comparative stabilizer CSt-1, which did notprovide any significant reduction in red Dmin. Coating 1-6 was preparedlike coating 1-2 except that to layer 1 was added 0.65 g/m² ofcomparative stabilizer CSt-2, which did not provide any significantreduction in red Dmin. Coating 1-7 was prepared like coating 1-2 exceptthat to layer 1 was added 0.65 g/m² of inventive stabilizer I-2, whichprovided lower red Dmin growth with 49° C. or 26° C. conditioning. Thelevel of I-2 provided more than enough Dmin reduction to compensate forincreased Dmin due to ambient radiation, as indicated by the `Delta RedDmin 12 wk/26° C. minus fresh` data. It is expected that the level ofthe stabilizer could be adjusted to provide zero Ddmin movement. Coating1-8 was prepared like coating 1-1 except that to layer 1 was added 0.65g/m² of I-2, which provides lower red Dmin growth with 49° C. or 26° C.conditioning. This result is in the absence of any added humectant. Thelevel of I-2 provided more than enough Dmin reduction to compensate forincreased Dmin due to ambient radiation, as indicated by the `Delta RedDmin 12 wk/26° C. minus fresh` data. It is expected that the level ofthe stabilizer could be adjusted to provide zero Dmin movement. Coating1-9 was prepared like coating 1-3 (no Dye-2) except that to layer 1 wasadded 0.65 g/m² of I-2, which did not provide any significant reductionin red Dmin. Therefore both the use of Dye-2 and the use of theinventive stabilizers is necessary to achieve the inventive results.Coating 1-10 was prepared like coating 1-2 and serves to provide ameasure of the repeatability in the reported data. Plus or minus 10% isan approximation. Coating 1-12 compared to coating 1-11 demonstrates thethe inventive combination works on cellulose acetate support as well ason polyethylene naphthalate support and whether or not there is presenta magnetic layer.

Comparative cyan dyes were as follows: ##STR14##

EXAMPLE 2

To a corona-discharge-treated polyethylene-2,6-naphthalene support,which was coated with a continuous subbing layer consisting of aterpolymer of n-butyl acryate, 2-aminoethyl methacrylate hydrochloride,and 2-hydroxyethyl methacrylate (50:05:45 wt ratio) at 0.317 g/m² ;deionized gelatin at 0.056 g/m² ; matte beads at 0.001 g/m² ; andsurfactant 10 G" (Dixie) at 0.012 g/m² ; the following layers wereapplied in the indicated sequence to produce Coating 2-1. The quantitiesquoted each relate to g/m². Emulsion sizes as determined by the disccentrifuge method are reported in Diameter x Thickness in microns. Theemulsions in the cyan layers are sensitized with dye set 1. Theemulsions in the magenta layers are sensitized with dye set 2. Theemulsions in the yellow layers are sensitized with sensitizing dye YD-A.

    ______________________________________                                        Layer 1                                                                              AntiHalation Undercoat                                                        Black colloidal silver    0.151                                               Gelatin                   1.61                                                Hexasodium salt of metaphosphoric acid                                                                  0.007                                               Disodium salt of 3,5,-disulfocatecol                                                                    0.18                                                Dye 1                     0.079                                               Dye 2 (D-2)               0.019                                               Oxidized developer scavenger O-2**                                                                      0.108                                               Dye-6                     0.077                                               Dye 3                     0.022                                               UV-1                      0.032                                               UV-2                      0.075                                        Layer 2                                                                              Slow cyan layer                                                               Tabular emulsion, 0.8 × .12, 4.1 mole % I                                                         0.33                                                Tabular emulsion, 0.5 × .08, 1.3 mole % I                                                         0.29                                                Gelatin                   1.36                                                Cyan dye forming coupler C-1                                                                            0.43                                                Bleach accelerator releasing coupler B-1                                                                0.054                                        Layer 3                                                                              Mid cyan layer                                                                Tabular emulsion, 1.1 × .12, 4.1 mole % I                                                         0.97                                                Gelatin                   1.35                                                Cyan dye forming coupler C-1                                                                            0.34                                                Development inhibitor releasing coupler DIR-1                                                           0.043                                               Bleach accelerator releasing coupler B-1                                                                0.032                                               Masking Coupler MC-1      0.011                                        Layer 4                                                                              Fast cyan layer                                                               Tabular emulsion, 1.4 × .12, 4.1 mole % I                                                         0.86                                                Gelatin                   0.97                                                Cyan dye forming coupler C-1                                                                            0.12                                                Development inhibitor releasing coupler DIR-1                                                           0.043                                               Masking Coupler MC-1      0.016                                               Yellow dye forming coupler Y-1                                                                          0.065                                        Layer 5                                                                              Interlayer                                                                    Gelatin                   0.43                                                Oxidized developer scavenger O-2                                                                        0.075                                        Layer 6                                                                              Slow magenta layer                                                            Tabular emulsion, 0.8 × .11, 2.6 mole % I                                                         0.38                                                Gelatin                   1.18                                                Magenta dye forming coupler M-1                                                                         0.27                                                Masking Coupler MC-2      0.043                                        Layer 7                                                                              Mid magenta layer                                                             Tabular emulsion, 1.1 × .12, 4.1 mole % I                                                         0.70                                                Gelatin                   1.16                                                Development inhibitor releasing coupler DIR-3                                                           0.016                                               Magenta dye forming coupler M-1                                                                         0.12                                                Masking Coupler MC-2      0.054                                        Layer 8                                                                              Fast magenta layer                                                            Tabular emulsion, 1.4 × .12, 4.1 mole % I                                                         0.75                                                Gelatin                   1.04                                                Development inhibitor releasing coupler DIR-4                                                           0.011                                               Magenta dye forming coupler M-1                                                                         0.053                                               Masking Coupler MC-2      0.043                                        Layer 9                                                                              Yellow filter layer                                                           Yellow filter dye AD-1    0.13                                                Gelatin                   0.65                                                Oxidized developer scavenger O-2                                                                        0.075                                        Layer 10                                                                             Slow yellow layer                                                             Tabular emulsion, 1.4 × .13, 4.1 mole % I                                                         0.25                                                Tabular emulsion, 1.1 × .13, 1.5 mole % I                                                         0.10                                                Tabular emulsion, 0.5 × .08, 1.3 mole % I                                                         0.15                                                Gelatin                   2.77                                                Yellow dye forming coupler Y-1                                                                          0.70                                                Yellow dye forming coupler Y-2                                                                          0.59                                                Development inhibitor releasing coupler DIR-6                                                           0.12                                                Development inhibitor releasing coupler DIR-3                                                           0.022                                               1,3 Butanediol            0.065                                               Bleach accelerator releasing coupler B-1                                                                0.005                                        Layer 11                                                                             Fast yellow layer                                                             Tabular emulsion, 2.9 × .13, 4.1 mole % I                                                         0.56                                                Gelatin                   1.50                                                Yellow dye forming coupler Y-1                                                                          0.18                                                Yellow dye forming coupler Y-2                                                                          0.15                                                Development inhibitor releasing coupler DIR-6                                                           0.057                                               Development inhibitor releasing coupler DIR-3                                                           0.006                                               Bleach accelerator releasing coupler B-1                                                                0.005                                        Layer 12                                                                             UV filter layer                                                               Silver bromide Lippmann emulsion                                                                        0.215                                               UV-1                      0.108                                               UV-2                      0.108                                               Gelatin                   0.699                                        Layer 13                                                                             Protective overcoat layer                                                     Colloidal silica          0.108                                               Gelatin                   0.882                                        ______________________________________                                    

Hardener(bis(vinylsulfonyl)methane at 1.50% of total gelatin weight).Unless otherwise noted, antifoggants (including4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene), surfactants, coating aids,emulsion addenda, sequestrants, lubricants, matte, tinting dyes, couplersolvents, and soluble absorber dyes were added to the appropriate layersas is common in the art. Magnetic recording layers were coated on thebackside of the support.

Coating 2-2 was prepared like coating 2-1 except that to layer 1 wasadded 0.67 g/m² of I-2.

Coating 2-3 was prepared like coating 2-1 except that to layer 1 wasadded 0.67 g/m² of CSt-3.

The results are shown in Tables II and III.

                  TABLE II                                                        ______________________________________                                                        Delta      Delta    Delta                                                     Red Dmin   Red Dmin Red Dmin                                                  8 wk/38° C.                                                                       12 wk/26° C.                                                                    12 wk/26° C.                       Coating         minus      minus    minus                                     #     Type      8 wk/-18° C.                                                                      12 wk/-18° C.                                                                   fresh                                     ______________________________________                                        2-1   Comparative                                                                             +.055      +.02     +.032                                     2-2   Invention +.007      -.002    +.003                                     2-3   Comparative                                                                             +.046      +.016    +.02                                      ______________________________________                                    

                                      TABLE III                                   __________________________________________________________________________             Delta                                                                         Red Dmin                                                                             Delta  Delta  Delta                                                    24 wk/26° C.                                                                  Red Dmin                                                                             Red Dmin                                                                             Red Dmin                                                 minus  24 wk/26° C.                                                                  52 wk/26° C.                                                                  52 wk/26° C.                                      24 wk/0-                                                                             minus  minus  minus                                           Coating #                                                                          Type                                                                              18° C.                                                                        fresh  52 wk/-18° C.                                                                 fresh                                           __________________________________________________________________________    2-1  Comp                                                                              +.032  +.042  +.065  +.104                                           2-2  Inv -.003  +.002  +.016  +.057                                           2-3  Comp                                                                              +.028  +.034  +.058  +.095                                           __________________________________________________________________________     8 wk/38° C. = Stored 8 weeks at 38° C. at 50% relative          humidity                                                                      8 wk/-18° C. = Stored 8 weeks at -18° C. at 50% relative        humidity                                                                      24 w/26° C. = Stored 24 weeks at 26° C. at 50% relative         humidity                                                                      24 w/-18° C. = Stored 24 weeks at -18° C. at 50% relative       humidity                                                                      52 w/26° C. = Stored 52 weeks at 26° C. at 50% relative         humidity                                                                      52 w/-18° C. = Stored 52 weeks at -18° C. at 50% relative       humidity                                                                 

The comparisons against a zero degree check are indications of a film'sinstability during storage under room or elevated temperatureconditions.

The comparisons against a fresh check are indications of a filmsinstability during storage under room or elevated temperatures and itssensitivity to ambient radiation.

Coating 2-1 features the use of Dye-2 in layer 1, and demonstrates highred Dmin growth with 49° C. conditioning. Coating 2-2 was prepared likecoating 2-1 except that to layer 1 was added 0.65 g/m² of I-2, whichprovides lower red dmin growth with 38° C. or 26° C. conditioning. Thelevel of I-1 provided enough dmin reduction to compensate for increasedDmin due to ambient radiation, as indicated by the `Delta RedDmin 12wk/26° C. minus fresh` and the `Delta RedDmin 24 wk/26° C. minus fresh`data. The `Delta RedDmin 52 wk/26° C. minus fresh` data showssubstantially lower red Dmin with the inventive combination on coating2-2. Coating 2-3 was prepared like coating 2-1 except that to layer 1was added 0.65 g/m² of CSt-3, which did not provide any significantreduction in red Dmin.

EXAMPLE 3

To a corona-discharge-treated polyethylene-2,6-naphthalene support,which was coated with a continuous subbing layer consisting of aterpolymer of n-butyl acryate, 2-aminoethyl methacrylate hydrochloride,and 2-hydroxyethyl methacrylate (50:05:45) at 0.317 g/m² ; deionizedgelatin at 0.056 g/m² ; matte beads at 0.001 g/m² ; and surfactant 10G"(Dixie) at 0.012 g/m² ; the following layers were applied in theindicated sequence to produce Coating 3-1. The quantities quoted eachrelate to g/m². Emulsion sizes as determined by the disc centrifugemethod are reported in Diameter x Thickness in microns. The emulsions inthe cyan layers are sensitized with dye set 1. The emulsions in themagenta layers are sensitized with dye set 2. The emulsions in theyellow layers are sensitized with sensitizing dye YD-A.

    ______________________________________                                        Layer 1                                                                              AntiHalation Undercoat                                                        Black colloidal silver    0.151                                               Gelatin                   1.61                                                Hexasodium salt of metaphosphoric acid                                                                  0.007                                               Disodium salt of 3,5,-disulfocatecol                                                                    0.18                                                Dye 1                     0.079                                               Dye 2                     0.019                                               Oxidized developer scavenger O-2                                                                        0.108                                               Dye-6                     0.060                                               Dye 3                     0.022                                               UV-1                      0.032                                               UV-2                      0.075                                        Layer 2                                                                              Slow cyan layer                                                               Tabular emulsion, 0.8 × .12, 4.1 mole % 1                                                         0.32                                                Tabular emulsion, 0.5 × .08, 1.3 mole % I                                                         0.28                                                Gelatin                   1.34                                                Cyan dye forming coupler C-1                                                                            0.43                                                Bleach accelerator releasing coupler B-                                                                 0.054                                        Layer 3                                                                              Mid cyan layer                                                                Tabular emulsion, 1.1 × .12, 4.1 mole % I                                                         0.97                                                Gelatin                   1.35                                                Cyan dye forming coupler C-1                                                                            0.34                                                Development inhibitor releasing coupler DIR-1                                                           0.043                                               Bleach accelerator releasing coupler B-1                                                                0.032                                               Masking Coupler MC-1      0.011                                        Layer 4                                                                              Fast cyan layer                                                               Tabular emulsion, 1.4 × .12, 4.1 mole % I                                                         0.86                                                Gelatin                   0.97                                                Cyan dye forming coupler C-1                                                                            0.12                                                Development inhibitor releasing coupler DIR-1                                                           0.043                                               Masking Coupkr MC-1       0.016                                               Yellow dye forming coupler Y-1                                                                          0.065                                        Layer 5                                                                              Interlayer                                                                    Gelatin                   0.43                                                Oxidized developer scavenger O-2                                                                        0.075                                        Layer 6                                                                              Slow magenta layer                                                            Tabular emulsion, 0.8 × .11, 2.6 mole % I                                                         0.38                                                Gelatin                   1.18                                                Magenta dye forming coupler M-1                                                                         0.27                                                Masking Coupler MC-2      0.043                                        Layer 7                                                                              Mid magenta layer                                                             Tabular emulsion, 1.1 × .12, 4.1 mole % I                                                         0.70                                                Gelatin                   1.16                                                Development inhibitor releasing coupler DIR-3                                                           0.016                                               Magenta dye forming coupler M-1                                                                         0.12                                                Masking Coupler MC-2      0.054                                        Layer 8                                                                              Fast magenta layer                                                            Tabular emulsion, 1.4 × .12, 4.1 mole % I                                                         0.75                                                Gelatin                   1.04                                                Development inhibitor releasing coupler DIR-4                                                           0.011                                               Magenta dye forming coupler M-1                                                                         0.053                                               Masking Coupler MC-2      0.043                                        Layer 9                                                                              Yellow filter layer                                                           Yellow filter dye AD-1    0.13                                                Gelatin                   0.65                                                Oxidized developer scavenger O-2                                                                        0.075                                        Layer 10                                                                             Slow yellow layer                                                             Tabular emuision, 1.4 × .13, 4.1 mole % I                                                         0.25                                                Tabular emulsion, 1.1 × .13, 1.5 mole % I                                                         0.11                                                Tabular emulsion, 0.5 × .08, 1.3 mole % I                                                         0.16                                                Gelatin                   2.77                                                Yellow dye forming coupler Y-1                                                                          0.70                                                Yellow dye forming coupler Y-2                                                                          0.48                                                Development inhibitor releasing coupler DIR-6                                                           0.12                                                Development inhibitor releasing coupler DIR-3                                                           0.022                                               1,3 Butanediol            0.065                                               Bleach accelerator releasing coupler B-1                                                                0.005                                        Layer 11                                                                             Fast yellow layer                                                             Tabular emulsion, 2.9 × .13, 4.1 mole % I                                                         0.56                                                Gelatin                   1.50                                                Yellow dye forming coupler Y-1                                                                          0.1 8                                               Yellow dye forming coupler Y-2                                                                          0.21                                                Development inhibitor releasing coupler DIR-6                                                           0.057                                               Development inhibitor releasing coupler DIR-3                                                           0.006                                               Bleach accelerator releasing coupler B-1                                                                0.005                                        Layer 12                                                                             UV filter layer                                                               Silver broniide Lippmann emulsion                                                                       0.215                                               UV-1                      0.108                                               UV-2                      0.108                                               Gelatin                   0.699                                        Layer 13                                                                             Protective overcoat layer                                                     Colloidal silica          0.108                                               Gelatin                   0.882                                        ______________________________________                                    

Hardener(bis(vinylsulfonyl)methane at 1.50% of total gelatin weight).Unless otherwise noted, antifoggants (including4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene), surfactants, coating aids,emulsion addenda, sequestrants, lubricants, matte, tinting dyes, couplersolvents, and soluble absorber dyes were added to the appropriate layersas is common in the art. Magnetic recording layers were coated on thebackside of the support.

Coating 3-2 was prepared like coating 3-1 except that to layer 1 wasadded 0.32 g/m² of I-2.

Coating 3-3 was prepared like coating 3-1 except that to layer 1 wasadded 0.65 g/m2 of I-2.

The results are shown in Tables IV and V.

                                      TABLE IV                                    __________________________________________________________________________             Delta  Delta  Delta  Delta                                                    Red Dmin                                                                             Red Dmin                                                                             Red Dmin                                                                             Red Dmin                                                 4 wk/49° C.                                                                   8 wk/38° C.                                                                   12 wk/26° C.                                                                  12 wk/26° C.                                      minus  minus  minus  minus                                           Coating #                                                                          Type                                                                              4 wk/-18° C.                                                                  8 wk/-18° C.                                                                  12 wk/-18° C.                                                                 fresh                                           __________________________________________________________________________    3-1  Comp                                                                              +.36   +.072  +.019  +.022                                           3-2  Inv +.22   +.049  +.006  +.011                                           3-3  Inv +.13   +.016  -.004  .00                                             __________________________________________________________________________

                                      TABLE V                                     __________________________________________________________________________             Delta  Delta  Delta  Delta                                                    Red Dmin                                                                             Red Dmin                                                                             Red Dmin                                                                             Red Dmin                                                 24 wk/26° C.                                                                  24 wk/26° C.                                                                  52 wk/26° C.                                                                  52 wk/26° C.                                      minus  minus  minus  minus                                           Coating #                                                                          Type                                                                              24 wk/-18° C.                                                                 fresh  52 wk/-18° C.                                                                 fresh                                           __________________________________________________________________________    3-1  Comp                                                                              +.043  +.039  +.064  +.083                                           3-2  Inv +.019  +.019  +.041  +.061                                           3-3  Inv +.010  +.004  +.018  +.037                                           __________________________________________________________________________

Coating 3-1 features the use of Dye-2 in layer 1, and demonstrates highred Dmin growth with 49° C. conditioning. Coating 3-2 was prepared likecoating 3-1 except that to layer 1 was added 0.32 g/m² of I-2, whichprovides lower red Dmin growth with 49° C., 38° C. or 26° C.conditioning. The level of I-2 can be adjusted as in coating 3-3 toprovide enough Dmin reduction to compensate for increased Dmin due toambient radiation, as indicated by the `Delta Red Dmin 12 wk/26° C.minus fresh` and the `Delta RedDmin 24 wk/26° C. minus fresh` data. The`Delta RedDmin 52 wk/26° C. minus fresh` data shows substantially lowerred Dmin with the inventive combinations in coatings 3-2 and 3-3, ascompared to coating 3-1.

Formulas for compounds used in the multilayers were as follows:##STR15##

The entire contents of the various patent applications, patents andother publications referred to in this specification are incorporatedherein by reference.

What is claimed is:
 1. A multilayer silver halide color negative photographic element comprising in the same layer a cyan dye of formula (I) and a ballasted stabilizer compound of formula (II), where the respective formulas are: ##STR16## wherein: R1 is selected from the group consisting of an alkoxy group, a phenoxy group and a halogen atom;R2 is selected from the group consisting of hydrogen, an alkyl group, a phenyl group; a halogen atom, an alkoxy carbonyl group of formula --COOR7, and a carbonamido group of formula --NR8COR7; R3, R4, R5 and R8 are independently selected from the group consisting of hydrogen and an alkyl group; R6 is an alkyl group; and R7 is an alkyl group or a phenyl group;and

    B--L--A--R                                                 (II)

wherein: B is a ballast group; L is a divalent linking group; A is a group of the formula: ##STR17## wherein R' is hydrogen or an alkyl or alkoxy group; and R is hydrogen or an aliphatic or aromatic group linked directly or through a nitrogen or oxygen atom to A.
 2. The element of claim 1 wherein R is selected from the group consisting of alkyl, aryl, alkoxy, aryloxy, alkylamido, arylamido groups.
 3. The element of claim 2 wherein R is an alkyl group.
 4. The element of claim 3 wherein the alkyl group is an unsubstituted group.
 5. The element of claim 1 wherein B is a group containing at least 6 carbon atoms.
 6. The element of claim 1 wherein B comprises a polymeric chain.
 7. The element of claim 6 wherein the polymeric chain is a polyalkylene group.
 8. The element of claim 7 wherein the polymeric chain is one obtained by polymerizing an acrylate or methacrylate monomer.
 9. The element of claim 1 wherein R4 is selected from the group consisting of methyl and sulfonamido ethyl groups.
 10. The element of claim 1 wherein L contains and is linked to B by a group selected from the group consisting of --C(O)O--, --C(O)NR'--, --CH₂ --, --O--, --NR'--, --OR'--, --OR'O--, --C(O)OR'O--, C(O)R'O--, and --C(O)N(R')R"O-- wherein each R' is independently hydrogen or an alkyl group and each R" is an independently selected alkyl group.
 11. The element of claim 10 wherein L is selected from the group consisting of --C(O)OCH₂ CH₂ O--, --C(O)OCH₂ CH₂ CH₂ O--, --C(O)NHCH₂ CH₂ CH₂ NH--, --C(O)OCH₂ CH₂ NH--, --C(O)OCH₂ C(CH₃)₂ O--, --C(O)OCH₂ C(CH₃)₂ CH₂ O--, --C(O)NHCH₂ CH₂ O--, and --C(O)OCH₂ CH(CH₃)O--.
 12. The element of claim 1 wherein B is a polymer having backbone molecular weight of greater than
 1000. 13. The element of claim 6 wherein the polymer is selected from polyvinyl, polyester, polyether, polyurethane, polyamide, polyacrylate, polymethacrylate and copolymers thereof.
 14. The element of claim 1 wherein the stabilizer is a polymer in which at least one wt. % of the polymer is derived from repeat units containing --L--A--R.
 15. The element of claim 14 in which --L-- is selected from the group consisting of --C(O)OCH₂ CH₂ O--, --C(O)OCH₂ CH₂ CH₂ O--, --C(O)NHCH₂ CH₂ CH₂ NH--, --C(O)OCH₂ CH₂ NH--, --C(O)OCH₂ C(CH₃)₂ O--, --C(O)OCH₂ C(CH₃)₂ CH₂ O--, --C(O)NHCH₂ CH₂ O--, and --C(O)OCH₂ CH(CH₃)O--.
 16. The element of claim 14 in which R is an alkyl group.
 17. The element of claim 1 wherein R2 is selected from the group consisting of an alkyl group, a phenyl group; a halogen atom, an alkoxy carbonyl group of formula --COOR7, and a carbonamido group of formula --NR8COR7.
 18. The element of claim 1 wherein R' is hydrogen.
 19. A process for forming a color negative image in the element of claim 1 after the element has been exposed imagewise to light, comprising contacting the exposed element with a color developing agent.
 20. The element of claim 1 wherein the color negative element contains a transparent support.
 21. A process for forming a positive image after imagewise exposing the element of claim 20 to light followed by developing the element to provide a color negative image, comprising optically printing said color negative image onto a second color negative element. 